Method of oxidizing hydrocarbon feeds employing discontinuous triggering means



INUOUS TRIGGER'ING MEAN j FiledNov.. 8.1960 v "wiLL-IAM BARTQK mvnronf METHOD oF oxmlzrNG HYDRocARBoN FEEDS Y :and reacted. The reaction may be further controlled A i by injecting line sprays of .water oran inert liquid ory EMPLOYING DlscoNrlNUoUs TRIGGERING MEANS' l Y William Bartok, Cranford, NJ., assignor to Esso Research and Engineering onipany, al corporation ofDelaware Filed Nov. 8, 1960,'Ser. No. 68,073 4- t 2 Claims. (Cl. 260-348.5)

, The invention relates to a method of initiating vapor phase oxidation reactions in-a reactor, hereinafter referred to as the homogeneousreactor, where rapid mixing of l the reactants, intermediates and products takes place to forma homogeneous .reaction mixture.' More specically,

difficult oxidation reactions are'initiat'ed or vtriggered in the homogeneous rea'ctorwithmoreeasily oxidizable substances and-then the .reaction `isallowedl to proceed in the absence of the initiator.'

' In the oxidation of organic compounds to useful products the reaction is arrested at the"partial oxidation stage. A quickl and thorough mixing of the reactants is vrequired toprevent the formation of localized hot spots e where the reaction can proceed to completion. Energy` released in the partial oxidation -of a hydrocarbon molecule accelerates its further oxidation unlessit lis quickly 'i dissipated. It is, therefore, of vital importance that the timeof reaction be limited as nearly *as possible to the minimum time necessary to achieve the desired conversion. 4 Various methods and means have been devised in the past. Among these isthe open tube reactor wherein unies of diluent and relatively low conversions per'pass. lA recent improvement-in this art is the raining solids reactor which makes use of a ne rain of inert solids falling down through the reaction zone, picking up lthe heat tion zone. v

It has'now been discovered that feeds thatcould not be oxidized or that could be oxidized only Aat very highl temperatures, i.e. above 11007 F., such as in the'case of ethane, will react with molecular oxygen at a ternperature below their oxidation threshold temperatures if a more easily oxidizable material is employed to initiate the reaction.

The process 'of the presentl invention is unique in vthat `the 'initiator' is utilized to start the reaction and oncey started, thereaction proceeds in the absence of additional initiator.v This process is not applicable, to other vapor phase partial oxidation methods in which lno extensive lbackmixing occurs. In the so-called initiated oxidations in.`.the prior art',.the addition of the initiator'must be continued throughout the reaction, otherwise the reac- -tion stops. Moreover, it is usually necessary to employ large quantities of the initiator so that in effectA it is part of the feed. In such processesI there is considerable product contamination vwhich makes separation and puri- .fication of the oxygenated products 'diicult and costly.v

These dilliculties` arenot'encountered in the present process because the initiator is not fed into the reactor onc the reaction is proceeding smoothly. In the reactor used to carry out the present invention,

control of. the reaction is maintained by continually back- -pacity or throughput.

tion and productselectivity.

In contrast to the raining solids reactor',r the hornos geneous reactor operates without solids flow. A preheated U oxygen-containinggas, e.g. air or molecular oxygen, and

' hydrocarbons are premixed, and fed into the reactor chamber of a reaction vessel together with a triggering- .agent at very high velocities, ire., a linear gas velocity ofuabout 10 to 5000 ft./second, through a series of tubular .conduits which are preferably nozzles or quills projecting into the reaction'chamber and having a'plurality of orilices. Preferably the oxidantand hydrocarbons are mixed in a mixing chamber by the action of hydrocarbon jets impinging into the oxidant stream.

' small hydrogen ame into the reaction chamber or heatvtemperature control is obtained by the use of large volliberated in thereaction4 and'carrying it out of the reac-` With an easily oxidizable-feed, the reaction may be initiated by preheating the lreaction vessel by a conventional heating means, e.g. by introducing a spark or `a ing the walls of the reaction chamber by electrical resistancel means. However,'when the feed is diflicultly oxidizable or cannot be oxidized under commercially feasible conditions, resort should be made to the use of easily oxidizable materials in accordance with the presentinvention. When this method is used, the triggering agent is introduced directly into the reaction chamber to contact the incoming reactants preheated to the oxidation threshold temperature of thetriggering agent. Once the reaction commences, the temperature can be lowered far below the initial reaction temperature caused in part bythe oxidation of the triggering agent while still maintaining v a high conversion withoutthe further addition ofthe triggering agent.

A suitable reactor for carrying out-the present process` is shown in the accompanying drawings.

FIGURE I is a sectional view of the apparatus taken i along theline A-A in FIGURE II. l

FIGURE 1I isa sectional viewof the samev apparatus taken along line B-B iny FIGURE I.

The reaction vessel may be a relatively smallhousing 'Y having a curved or polygonal internal surface that will permit the gaseous reactants to swirl in a generally It'ii'r-y cular concurrent motion; The reactor operates most edi- -ciently whenthe conduits are so positioned as to concurrently discharge the streams l of gaseous mixture tangentially to the path of the swirling mixture to impart to said mixture' the desired constantly swirling motion.

The gases swirl past each nozzle orifice and are continually mixed with the cooler fresh reactants `which 'tend mixing and quenching the reacting mass with relatively cool incoming reactants 'while' simultaneously removing reaction products from the reaction zone for nal quench,-

to serve as a brake on the reaction.

or gaseous coolant directly into the reaction chamber.' to

aid in temperature control or the reaction vessel itself may be immersed in a coolant.

Exit means are provided through which the products of n reaction are continuously removed from the reactionvessel by virtue of the pressure dropacross the reactor.

vPatented Aug.- 18,".1964

The y. major advantagesof thehomogeneous reactor are its ex `treme mechanical simplicity, short' residence time, -i.'e.,

The homogeneous reactoralso offers certain advantages in quenching, adiabatic operaf Additionaimbuiar nozzles or coolant conduits having a plurality o f orifices may be used to release a spray of water or an 'inert liquid In a reactor of the type just described certain opposing forces must be recognized and controlled. To obtain short residence times and at the same time provide adequate backmixing to self-perpetuate and control the reaction,

- face first contacted by reactants leaving the reactant into C, aldehydes and ketones are also effective in the present process. Among the aliphatic saturated ketones and aldehydes that can be utilized to trigger reactions are acetaldei hyde, butyraldehyde, acetone, methylethyl ketone, n-valeraldehyde and caproaldehyde.

The more difficultly oxidizable feeds include the low i molecular weight parans and olefns, as well as thefunsubstituted cyclic parains and aromatica. Generally, the

lets, low residence times may be maintained but adequate Y backmixing will not be accomplished.- 1f, ,on the other hand, the location of the exit openings causes excessive backmixing, the residence time increases and there is a corresponding loss of product selectivity. The exit means in the homogeneous reactor is, therefore, centrallyposi tioned in relation to a surfaceother than the concave surface first contacted by reactants leaving the reactant inlets.

The reactant inlets are spaced away from both the aforechamber into which the reactants and reaction products spiral toward a vortex before leaving via the exit means.

' In accordance with the present invention, about 1 to 100 mole percent (based on the reactant feed) of a more easily oxidizable organic substance is used to initiate partial oxidation reactions in the'above-described homogeneous reactor. Even when relatively small amounts, e.g.' 10 to 50 mole percent, of the more easily oxidizable substance or triggering agent are used to initiate the reaction, it is possible to lower the oxidation threshold temperature of the reactant up to several hundred degrees. By means of the present invention, a feed, such as ethane, can be partially oxidized with molecular oxygen, e.g. air, under controlled conditions. far below its normal oxidation threshold temperature.

The oxidation initiator triggers the vapor phase reaction and thereafter the reaction continues without the initiator. The reaction is sustained because the contents of the reactor are well mixed and therefor the free radicals that are formed can propagate the reaction. The reaction temperature generally rises substantially during the initiation period, which is usually no more than a few minutes, due to the vigorous oxidation of the triggering agent. Thereafter the triggering agent is shut off and the reaction mixture is cooled until optimum selectivity and conversion are obtained. The finaltemperature is normally several hundred degrees below the normal oxidation threshold temperature of the reactant.

The present invention has two principal advantages,` namely it allows one vto partially oxidize feeds that are otherwise hard to oxidize at lower temperatures and provides a method wherein the products are not contaminated by the triggering agent `or its oxidation products.

The selection of the triggering agent depends mainly upon the reactant and the process conditions. Generally speaking, moderately high molecular weight straight and branched chain paraffins and olens are excellent initiators, especially for low molecular weight paratins and olefns. Among the olefins and parafiins suitable for use as initiators are C to Cm olefins such as heptene-l, pentene-2, Z-methyl hexene-l, nonene-l and decene-l, and C5 to C paraffins such as n-hexane, isooctane, n-decane and n-heptane. The preferred olefins and parains have 6 to 8 carbons, e.g. n-hexane.

In addition to the hydrocarbon initiators listed above,

`has been triggered with n-hexane.

feeds do not contain compounds having more than 10 or l2 carbon atoms. f

Paraffins, both straight chain and branched, containing up to 4 carbon atoms per molecule are usually quite difcult to oxidize without resorting to very high pressures andtemperatures. This is especially true of methane,

' ethane and propane, and to a lesser extent of butane and isobutane.

Among the olefin feeds that can be oxidized in accordance with the present invention are the C, to C; com- 4 pounds, such as ethylene and the butenes.

Suitable cycloparafiin feeds include C, to C. hydro carbons such as cyclopropane, cyclopentane and cyclohexane. Aromatics, such as benzene, and methylated aromatics, e.g. toluene, xylenes, durene and mesitylene, are also not easily oxidizable and therefore can be used as feeds in the present process.

The oxidant is usually adilute oxygen stream, such as air or oxygen mixed with nitrogen. The oxidant-hydrocarbon feed molar ratio should be maintained between about 0.1 to 5:1.

The reaction time is conrolled by the rate of throughput. The degree of conversion per pass, the amount of preheating involved and the employment of extraneous coolants all affect the temperature. Pressure is controlled by throttling or exhausting the exit line. For a given oxidant/hydrocarbon ratio, an optimum time-temperaturepressure combination can be selected to give high oxygen utilization per pass while minimizing the formation of carbon oxides and water. Once the reaction is triggered less preheating is necessary. At low conversions the reaction temperature can be controlled by feed temperature, i.e. the heat of reaction can be dissipated by heating the fresh feed to reaction temperature.

As soon as the oxidation is triggered, the residence time is decreased to the desired level. For instance, residence times .of about 0.05 to 3.0 seconds have been found suitable after the oxidation of low molecular weight parans Residence times of 0.6 to 2.0 seconds are preferred. Once the addition of the triggering agent is ceased, the reaction is allowed to proceed at temperatures of about 500 to about 1000 F.,

preferably 600 to 800 F., and the initial residence time is reduced, e.g. from about 1 to 10 seconds to about 0.05 to 3 seconds. The hot swirling reactants are continuously mixed with the cooler incoming reactants preheated to about the aforementioned temperatures. When additional cooling is desired, fine sprays of water or an inert liquid or gaseous coolant may be introduced into the reaction chamber. The reactor may be operated with pressures of about 0 to 500 p.s.i.g., preferably 40 to 100 p.s.i.g., in the reaction chamber. However, for proper mixing and throughput, the feed should be introducedl under pressure, i.e. at least 20 p.s.i.g. Superatmospheric pressures are beneficial because they promote the oxidation and permit the use of even lower temperatures.

Referring now to FIGURES I and II in the accompanying drawing, the present process is carried out by initially introducing the feed and a small amount of a triggering agent, preheated to above the oxidation threshold temperature of the triggering agent but below the threshold temperature of the feed, into mixing chamber 2 via a perforated tube 1. Any suitable means for injecting a large number of small gaseous streams into the mixing chamber may be employed. The gaseous feed leaving tube 1 impinges on and admixes with a stream of air preheated to the aforementioned temperature, which t 'i ac Yields of Liquid Products:

stream enters chamber 2 via oxidant inlet 3. The mixed kgases then pass into .aseries of multicrice nozzles 5 that communicate with chamber 2 and project into reaction chamber 4 which is formedby a curved orconcave wall andflat walls 11 and 12.A The feed nozzles'S penetrate wall 12 andcommunicate with mixing chamber 2. Cooling liquid or gas'e.g..water, may be introduced 'into reaction chamber 4 through a plurality of multi-orifice cooling nozzles 6 which penetrate wall 11. A perforated cylinder 7 is centrally located in the reaction chamber 4` to regulate the'ow of the reaction products leaving 'the reactor via exit tube 8. Quenching inlets 9 communicating with tube .8 are provided for introducing water or other liquid or gaseous quenching substances into the exit tube. Within a few seconds the temperature of the swirling reaction mixture commences-to rise and -after about 5 to 10 minutes the :iiowof the triggering agent into the. reactor is stopped and the reaction is continued solely by the introduction o fthe feed and air at a vtemperature below the ordinary'oxidation threshold-'of vthe feed.

. 6 1 selectivity with respect to useful organic oxygenated products, such as formaldehyde, acetaldehyde -aud ethanol.

These products, as well as-ethylene which is also formed.' y

during the reaction, have a wide'utilization in the chemical eld as monomers, diluents, etc.

EXAMPLE 2 Isobutylene is not partially oxidized by airin the homogeneous reactor even at temperatures exceeding 1000* F.

However, the partial oxidation of -isobutylene proceeds smoothly at temperaturesbelow -900 P. at an oxygen/ isobutylene mole ratio of approximately l when 'the process is triggered with heptene-l. For example, a substantially complete conversionl o f oxygen is obtainedv at a pressure of p.s.i.g. and a' temperature of 820 P.

' 'when the reaction is triggeredwith 40 mole'percent heptene-l (based on the isobutylene).

The following examples provide. a better understanding.

l v EXAMPLE 1 v Ethane cannot be partially oxidized with oxygen in the homogeneousreactor described above even at temperatures up to 1100o F. However, when the ethane oxi#4 percent n-hexane (based on the ethane) lto the ethaneoxygen mixture until the reaction started and thereafter '.-for about 5 to 10 minutes. Under these conditions about 25% of the eth'ane and 85% of the oxygen fed into the homogeneous reactor reacted. The reaction product consisted principallyv of ethylene and formaldehyde with some acetaldehyde and formic acid being formed.

The-followingis a series of runs carried out under varil l ous conditions showing the eiectof reducing the final. reaction temperature and increasing the pressureon the reaction products.

Air Oxidation of Ethane-in Homogeneous Reactor Trgv,gered Withv25 lMole 'Percent` n- Hexne (Based on Edurne)v f f [o2/ethnie melamine-0.5]

Run N0 1 2 3 4 Pressure, p.s.i.g v20 20 50 50 Temperature, F 1, 100 1,128 988 940 Initial Residence Time, sec... x 2 2 2 2 Final Residence Time, sec 0. 74 0. 73 1. 50 1. 55 Conversions:

- Ethane Conversion, wt. percent l. 37. 7 43. 1 29. 8 25. 6 Oxygen Conversion, wt. percent. 99. 0 100. 0" 99. 3` 86. 7 Moles Og/Moles Ethan@ Reacted. 1. 32 1.16 1. 67 1. 70 Yields of Gaseous Products:

Moles Ethylene Made/Mole Ethane Reaeted-'.. 0 622 0.602 0 578 0. 622

Moles CO Made/Mole Eth e Reacted 0.503 0.521 0.571 0.502

' Moles CO; Made/Mole Ethane R6 teil.;

zO/g. Ethane Reaeted v0. 490 1.653 2.000 2.051 g. Liquid Organic Oxys/g. Eth- 1 Based on carbon balance. V

The initial residence time is about 2 seconds and the final residence time is about 1 second. Under the'se conditions, about 30% of the isobutylene and 90%' of the oxygen in the air reacted. The reactionr products are mainly watersoluble loxygenated products', such as isobutylene oxidev and formaldehyde, and lowermolecular weight olelins, such as. ethylene and propylene. -Waterand some carbon oxides are also produced.

EXAMPLE3 Propylene, which isdiliicult :to oxidize in the homogene- .I

ous reactor evenat temperatures exceeding 1100" F., can be partially oxidized with air Vat temperatures below 1000 F. when the reaction istriggered with methanol. For example, the oxygen (oxygen/propylene mole ratio is about 0.5) in the air supplied to the reactor is substantially completely converted at a pressure of 100 p.s.i.g. and a temperature of 920". F. when the ,oxidation is triggered with 5 mole percent methanol (based on the propylene).

The initial residence time is about 2 seconds andthevnal residence time is about 1 second. Under these conditions', about'25% of the propylene and 80% of theoxygen in l the air` reacted. The reaction products are mainly acet- -aldehyde, propionaldehyde, formaldehyde and'ethylene, l

` with some acetone also produced. f

The above-described method provides an ecient and inexpensive method for oxidizing those feeds which are otherwise dificult or impossible to oxidize. The triggering agent permits the use of lower temperatures which have been shown to favor selectivity tocertain desirable oxygenated products and also increases throughput by reducing the residence time which would otherwise be necessary `to oxidize some of the feeds. Perhaps the greatest advantage of the present process is that the triggering agent need not be fed to the reaction zone once .the oxidation commences. That is to say, the triggering agent provides a condition under which the chain reaction is self-propagating even at moderately high temperatures.

It is not intended to restrict the present'invention tothe foregoing embodiment, but rather it should only be limited by the' appended claims in which' it. is intended to claim all the novelty inherent in'the invention.

What is claimed is: 1. In a process for oxidizing a hydrocarbon feed selected from the group consisting of C1 to C4 paran, C2

to C4 monoolens, C3 to C5 cycloparains and aromatic hydrocarbons containing up to l0 carbon atoms in which the feed is mixed with molecular oxygen-containing'gas and the resultant mixture is preheated to a temperature between about 500 and 1000 F. and continually passed into a reaction zone at a pressure between about 20 and 500 p.s.i.g. and at a linear gas velocity of about 10 to 5000 ft./second so asA to impart a swirling motion to said mix ture whereby fresh incoming feed is back-mixed with at least a portion of the oxidation yproduct formed in said reaction zone andv oxidation products are continuously withdrawn from said zone after a residence time therein of about 0.01 to 10 seconds, -the improvement which feed and selected from the group consisting of C5 to C10 parafns, VC5 to C10 monoolens, C, to C, organic alcohols, and C2 to C6 carbonyl compounds into said reaction zone at a temperature below the threshold oxidation temperature of said hydrocarbonfeed butat least equalto the threshold oxidation Atemperature of said triggering agent, ceasing to introducethe triggering agenLinto the 10 reaction zone after the hydrocarbon feed commences to oxidizeand thereafter oxidizing said feed in the absence of additional triggering reagent at a temperature below the ordinary oxidation threshold temperatureof said hydrocarbon feed.

2. A' process according to claim 1 in which the triggering agent is n-hexane and the feed is a C1 to C, parain.

References Cited in the le of this patent UNITED STATESY PATENTS 2,018,994 Burke et al.. Oct. 29, 1935 2,270,780 Berl Ian. 20, 1942 2,530,509 Cook Novl 21, '195o 2,689,253 Robertson et al Sept. .14, 1954 2,727,919 Saunders Dec. 20,1955 2,769,846 Di Nardo et al. Nov. 6, 1956 2,974,173 Long et al Mar. 7, 1961 2,981,747

' Lang et al Apr. 25, 1961 

1. IN A PROCESS FOR OXIDIZING A HYDROCARBON FEED SELECTED FROM THE GROUP CONSISTING OF C1 TO C4 PARAFFIN, C2 TO C4 MONOOLEFINS, C3 TO C6 CYCLOPARAFFINS AND AROMATIC HYDROCARBONS CONTAINING UP TO 10 CARBON ATOMS IN WHICH THE FEED IS MIXED WITH MOLECULAR OXYGEN-CONTAINING GAS AND THE RESULTANT MIXTURE IS PREHEATED TO A TEMPERATURE BETWEEN ABOUT 500* AND 1000*F. AND CONTINUALLY PASSED INTO A REACTION ZONE AT A PRESSURE BETWEEN ABOUT 20 AND 500 P.S.I.G. AND AT A LINEAR GAS VELOCITY OF ABOUT 10 TO 5000 FT./SECOND SO AS TO IMPART A SWIRLING MOTION TO SAID MIXTURE WHEREBY FRESH INCOMING FEED IS BACK-MIXED WITH AT LEAST A PORTION OF THE OXIDATION PRODUCT FORMED IN SAID REACTION ZONE AND OXIDATION PRODUCTS ARE CONTINUOUSLY WITHDRAWN FROM SAID ZONE AFTER A RESIDENCE TIME THEREIN OF ABOUT 0.01 TO 10 SECONDS, THE IMPROVEMENT WHICH COMPRISES TRIGGERING THE OXIDATION OF SAID FEED BY INITIALLY INTRODUCING A TRIGGERING AGENT COMPRISING A MORE EASILY OXIDIZABLE ORGANIC COMPOUND RELATIVE TO SAID HYDROCARBON FEED AND SELECTED FROM THE GROUP CONSISTING OF C5 TO C10 PARAFFINS, C5 TO C10 MONOOLEFINS, C1 TO C4 ORGANIC ALCOHOLS, AND C2 TO C6 CARBONYL COMPOUNDS INTO SAID REACTION ZONE AT A TEMPERATURE BELOW THE THRESHOLD OXIDATION TEMPERATURE OF SAID HYDROCARBON FEED BUT AT LEAST EQUAL TO THE THRESHOLD OXIDATION TEMPERATURE OF SAID TRIGGERING AGENT, CEASING TO INTRODUCE THE TRIGGERING AGENT INTO THE REACTION ZONE AFTER THE HYDROCARBON FEED COMMENCES TO OXIDIZE AND THEREAFTER OXIDIZING SAID FEED IN THE ABSENCE OF ADDITIONAL TRIGGERING REAGENT AT A TEMPERATURE BELOW THE ORDINARY OXIDATION THRESHOLD TEMPERATURE OF SAID HYDROCARBON FEED. 